CN103430089A - Electrochromic device with anti-iridescent coating - Google Patents
Electrochromic device with anti-iridescent coating Download PDFInfo
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- CN103430089A CN103430089A CN2011800405996A CN201180040599A CN103430089A CN 103430089 A CN103430089 A CN 103430089A CN 2011800405996 A CN2011800405996 A CN 2011800405996A CN 201180040599 A CN201180040599 A CN 201180040599A CN 103430089 A CN103430089 A CN 103430089A
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- Prior art keywords
- control coating
- reflex control
- counter substrate
- coating
- laminated
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/157—Structural association of cells with optical devices, e.g. reflectors or illuminating devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
- B32B17/10201—Dielectric coatings
- B32B17/10211—Doped dielectric layer, electrically conductive, e.g. SnO2:F
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10431—Specific parts for the modulation of light incorporated into the laminated safety glass or glazing
- B32B17/10467—Variable transmission
- B32B17/10495—Variable transmission optoelectronic, i.e. optical valve
- B32B17/10513—Electrochromic layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/1077—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyurethane
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/225—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
- G02F2201/38—Anti-reflection arrangements
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Laminated Bodies (AREA)
- Joining Of Glass To Other Materials (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The invention relates to a device (1) of the electrochromic type comprising successively a substrate (2), a reflection control coating (8), a laminating interlayer (10), a functional system (4) of the electrochromic type and a substrate (2). This particular arrangement of the laminating interlayer between the reflection control coating and the functional system and the choice of the refractive index and thickness of the reflection control coating are such that the saturation values of C* in the colorimetric system (L*, a*, b*) of the device in reflection are less than or equal to 10 for angles of incidence of 60 DEG and 8 DEG relative to the normal (N) to the outer face (6B) of the counter-substrate and that the absolute value of the difference between the value of C* at an angle of incidence of 8 DEG and the value of C* at an angle of incidence of 60 DEG is less than or equal to 6.
Description
The present invention relates to have can be automatically controlled optics and/or the field of electrochemical devices of energy characteristics.
Under the effect that the present invention relates to supply with at suitable electricity, some characteristic, particularly under some electromagnetic radiation wavelength, especially transmission under visible and/or infrared or light scattering, absorption, the changeable device of reflection.Transmission changes and usually to betide described optical region (infrared, visible, ultraviolet) and/or other electromagnetic radiation zone, so that this device has variable optics and/or energy characteristics, and described optical region must not be unique zone related to.
About heat, the glass pane that transmission/absorption can change under at least a portion solar spectrum (glass pane) makes when they are installed to be the outer glass part of building or during as the window of the type means of transports such as automobile, train, aircraft, can control the sunlight input to house interior or vehicle interior/compartment, and prevent by this way its superheated under strong daylight.
About the optics aspect, they make visual degree to be controlled, and this makes when they are installed to be the outer glass part in strong daylight situation, and it can prevent dizzy.They also can have the useful especially effect of blocking, not only as the outer glass part but also for the inner glass part, for example, for equipping indoor partition (office of building) between room or for example for separating the compartment of train or aircraft.
Yet outwards these devices of reflex time have the shortcoming that causes add lustre to (coloration) usually.In order to overcome this defect, WO-A-00/03290 has instructed adding lustre under change/reflection attenuation, i.e. colorimeter system (L
*, a
*, b
*) middle C
*The coating setting of intensity value, it has the thin layer of at least one refractive index between 1.6 and 1.9.
For example, WO-A-00/03290 has instructed between described external substrate and electrochromic system, has refractive index and be 1.7 and the setting of the layer of the thickness SiOC that is 50-55nm.This functional system, and is contacted with the latter by this way by Direct precipitation on the SiOC layer, and it is preferred by instruction.
Yet, although be enhanced with adding lustre in the reflection of normal incident, in incident angle situation that ought be less, this adds lustre to be proved to be still and exists, for example, with respect between 15 °-60 ° of normals.
An object of the present invention is to provide a kind of have can be automatically controlled optics and/or the electrochemical appliance of energy characteristics, the less that adds lustre in its reflection, significantly under the colored state of this device, and this is not only for normal incident angle (0 °), too for higher incident angle (between 15 °-60 °).
For this reason, theme of the present invention is the device of described type, and it comprises:
-substrate;
-have can be automatically controlled optics and/or the electrochemical function system of energy characteristics, this function system comprises:
The first electrode coating formed on substrate;
The second electrode coating; With
At least one electrochemical activity layer, its between the first electrode coating and the second electrode coating, at least one active electrochemical layer can the first state and and the first state there is different optical and/or energy and transmit between the second state of performance and reversibly change.
-counter substrate (counter-substrate), it is designed to be arranged on the outside of incident sunlight one side with respect to substrate;
-reflex control coating, it is for decaying/change lateral reflection device color outwardly; The reflex control coating forms on the inside surface of counter substrate, and the reflex control system plays the colorimeter system (L that reduces device described in reflection
*, a
*, b
*) middle C
*The effect of intensity value;
-laminated middle layer, it is made by polymeric material, and insert between reflex control coating and functional system, counter substrate and laminated middle layer have the refractive index between 1.4-1.7, and are greater than 20 μ m, for example are greater than the thickness of 100 μ m, for example, for laminated middle layer, its thickness is greater than 300 μ m, and, for example for counter substrate, its thickness is greater than 500 μ m
Select refractive index and the thickness of reflex control coating, C when to make incident angle with respect to the normal of the outside surface of counter substrate be 60 ° and 8 °
*Be less than or equal to 10, and the C of incident angle while being 8 °
*C when value and incident angle are 60 °
*The absolute value of the difference of value is less than or equal to 6.
According to the present invention, the reflex control coating by bi-material (counter substrate and laminated middle layer) around, the refractive index of this bi-material is between 1.4-1.7, and thickness is much larger than the wavelength (between 0.4-0.8 μ m) of visible region.These characteristics are in conjunction with the suitable selection to reflex control coating refractive index and thickness, have the described device minimum effect that adds lustre in reflection of giving, significantly with respect to the high incident angle of normal.
According to a particular, also comprise one or more following technical characterictics according to device of the present invention, adopt separately or adopt all technical in combination possible:
-select refractive index and the thickness of reflex control coating, the C while making incident angle with respect to the normal of counter substrate outside surface between 8 °-60 °
*For being less than or equal to 10;
-reflex control coating comprises the individual layer of material;
The inside surface of-reflex control coating contact counter substrate;
-reflex control coating contacts the outside surface in laminated middle layer;
-reflex control coating comprises that refractive index is between 1.6-2.4, preferably between 1.75-2.15, and the preferred layer between 1.90-2.05;
The thickness of-reflex control coating is between 60-110nm, preferably between 60-90nm;
The reflection coefficient of-reflex control coating is more than or equal to 10%, preferably between 12-25%;
-reflex control coating consists of one or more materials, and described material is selected from following: several combination in the titanium dioxide of the indium oxide of silicon nitride, tin oxide, silicon oxynitride, zinc paste, aluminium nitride, doped tin (ITO), tin/zinc mixed oxide, titanium dioxide, doping zinc, the titanium dioxide of mixing silicon or these materials;
The refractive index of-counter substrate is between 1.45-1.60;
The refractive index in-laminated middle layer is between 1.45-1.60;
-laminated middle layer is the film that thermoplastic forms, for example, by PU (polyurethane), PVB, acoustics PVB, EVA or SGP (DuPont SentryGlas
Plus) make;
-functional system is electrochromic system, and at least one electrochemical activity layer is that electricity causes and adds lustre to;
-electrochromism functional system has solid-state type.
In addition, a theme of the present invention is glass workpiece, and wherein it comprises at least one sheet with glass workpiece function, and wherein glass workpiece comprises device as above, and substrate and counter substrate are the sheets with glass workpiece function.
In addition, an object of the present invention is a kind of method of manufacturing installation, it comprises the following steps:
-formation the first electrode coating on substrate;
-form the second electrode coating;
-form at least one electrochemical activity layer, its between the first electrode coating and the second electrode coating, at least one active electrochemical layer can the first state and and the first state there is different optical and/or energy and transmit between the second state of performance and reversibly change;
-formation reflex control coating, it is for changing/decay the color of lateral reflection outwardly, the reflex control coating forms on the inside surface of counter substrate, counter substrate is designed to be arranged on the outside with respect to substrate of incident sunlight one side, and the reflex control coating plays the colorimeter system (L that reduces device described in reflection
*, a
*, b
*) middle C
*The effect of intensity value;
-laminated the middle layer that will be made by polymeric material is for laminated counter substrate, laminated middle layer is between reflex control coating and functional system, counter substrate and laminated middle layer have the refractive index between 1.4-1.7, with be greater than 20 μ m, for example be greater than the thickness of 100 μ m, for example, for laminated middle layer, its thickness is greater than 300 μ m, and for example for counter substrate, its thickness is greater than 500 μ m
C when to select the refractive index of reflex control coating and thickness to make incident angle with respect to the normal of the outside surface of counter substrate be 60 ° and 8 °
*Be less than or equal to 10, and the C of incident angle while being 8 °
*C when value and incident angle are 60 °
*The absolute value of the difference of value is less than or equal to 6.
According to a particular, preparation in accordance with the present invention also comprises one or more following technical characterictics, adopts separately or adopt all technical possible combinations:
-select refractive index and the thickness of reflex control coating, make the C of incident angle between 8 °-60 ° for the normal of counter substrate outside surface
*For being less than or equal to 10;
-deposition materials individual layer is to form the reflex control coating;
-by reflex control coating Direct precipitation on the inside surface of counter substrate;
-laminated middle layer directly is placed on the reflex control coating;
The refractive index of the layer of-formation reflex control coating is between 1.6-2.4, preferably between 1.75-2.15, preferably between 1.90-2.0;
The thickness of-reflex control coating is between 60-110nm, preferably between 60-90nm;
The reflection coefficient of-reflex control coating is more than or equal to 10%, preferably between 12-25%;
The layer of-formation reflex control coating consists of one or more materials, and described material is selected from following: several combination in the titanium dioxide of the indium oxide of silicon nitride, tin oxide, silicon oxynitride, zinc paste, aluminium nitride, doped tin (ITO), tin/zinc mixed oxide, titanium dioxide, doping zinc, the titanium dioxide of mixing silicon or these materials;
The refractive index of-counter substrate is between 1.45-1.60;
The refractive index in-laminated middle layer is between 1.45-1.60;
-laminated middle layer is the film consisted of thermoplastic, for example by PU (polyurethane), is made;
-functional system is electrochromic system, and at least one electrochemical activity layer is electrochromic;
-electrochromism functional system has solid-state type.
With reference to accompanying drawing, by the description be merely given as examples below reading, the present invention will be better understood, and wherein Fig. 1 is a schematic sectional view according to electrochemical appliance of the present invention.
Due to differing greatly between the difference of thickness, particularly substrate and sedimentary deposit, be for example the magnitude of 500 times, clear for what explain, this figure does not obviously draw in proportion.
Shown device 1 comprises the counter substrate 6 of substrate 2, functional system 4 and defencive function system 4.
Functional system 4 is electrochromic systems, by applying electric field, reversibly controls the system of transmittance, but it more generally comprise have can be automatically controlled optics and/or the modification of the electrochemical appliance of energy characteristics.
Functional system 4 forms at least in part on substrate 2, that is to say, it comprises the layer that at least one forms on substrate 2.
" the layer A of the upper formation of layer B (or deposition) " is interpreted as in the text layer A and directly forms on layer B, and with layer B, contacts thus, or layer A forms on layer B by one or more layers embolus between layer A and layer B.
Counter substrate 6 is designed to defencive function system 4.It is arranged on the outside of incident sunlight one side with respect to substrate 2.
Device 1 also comprises: reflex control coating 8, and it is for decaying/change the color of the device 1 of lateral reflection outwardly, and laminated middle layer 10 made by polymkeric substance, and it inserts between functional system 4 and reflex control coating 8.
Reflex control coating 8 is formed on the inside surface 6A of counter substrate 6.Its Direct precipitation, on the latter, and contacts with the inside surface 6A of counter substrate 6 by this way.
C when to select the refractive index of reflex control coating 8 and thickness to make incident angle with respect to the outside surface 6B normal N of counter substrate 6 be 60 ° and 8 °
*Be less than or equal to 10, and the C of incident angle while being 8 °
*C when value and incident angle are 60 °
*The absolute value of the difference of value be less than or equal to 6 (| C
* 8 °-C
* 60 °|≤6).
Select 8 ° of angles so that measure, but the C when this incident angle
*The C obtained when value and 0 °
*Be worth very approaching.Mensuration when 0 ° of angle is actual is very difficult.
With respect to the whole interval of 8 ° and 60 °, also select 60 ° and 8 ° of these two values so that measure, but the effect obtained is this specific character had for the numerical value between all 8 ° and 60 °.
Found the selection of described Plant arrangement, particularly functional system 4, and the positioned opposite of laminated middle layer 10 and reflex control coating 8 can make the color in reflection to be controlled, significantly with respect to the high incident angle of normal.
The color of installing in reflection is actually due to long interference the mutually in the reflection in certain wavelength coverage, generally close to redness, makes this glass workpiece be pink colour, significantly with respect to the high incident angle of normal.
In conjunction with the specific selection of the material of reflex control coating 8 and change the layout of described device, this can obtain required result.
As explained above, according to the present invention, reflex control coating 8 be by the material of two kinds of refractive indexes between 1.4-1.7 around.Counter substrate 6 and laminated middle layer 10 also have the thickness that is greater than 20 μ m, so it is much larger than 1 μ m, much larger than the wavelength (0.4-0.8 μ m) of visible region.These characteristics are in conjunction with the suitable selection of reflex control coating 8 refractive indexes and thickness, there is constructive interference in the reflection of control, and realize by this way installing the 1 less effect added lustre to for the approaching incident angle of normal with for being in the reflection of larger incident angle with respect to normal.
Therefore reflex control coating 8 preferably includes refractive index between 1.6-2.4, preferably between 1.75-2.15, more preferably at the layer of 1.90-2.05.
The thickness of reflex control coating 8 is between 60-100nm, preferably between 60-90nm.
Refractive index in it should be noted that in full is interpreted as the refractive index under 550nm.
Because the selection of material is very special, contrary with WO-A-00/03290, this has optimized the reflex control coating in order to reduce reflection (antireflection effect).Select coating of the present invention for reflected light, in order to control for long interference the mutually in the reflection of wide-angle scope.
Therefore reflex control coating 8 has the reflection coefficient that for example is more than or equal to 14%.
Coating 8 one or more materials based on from following selection for example: several combination the titanium dioxide of the indium oxide of silicon nitride, tin oxide, silicon oxynitride, zinc paste, aluminium nitride, doped tin, the tin/zinc oxide of mixing, titanium dioxide, doping zinc, the titanium dioxide of doped silicon, zirconia or these materials.
Advantageously, coating 8 comprises for example Si of thickness between 60-90nm
3N
4Layer.
This layer has approximately 2.02 refractive index.
It should be noted in the discussion above that for nitrogen Si
3N
4The nitrogen of layer must not be stoichiometry, that is to say that the nitrogen-atoms ratio must not be 4/3.For example this layer is hyperstoichiometry or substoichiometric.
Advantageously, coating 8 comprises single layer of material, for example Si
3N
4Individual layer.
Advantageously, coating 8 contacts with the inside surface 6A of counter substrate 6 and/or contacts with the outside surface 10B in laminated middle layer 10.
Counter substrate 6 is the sheets with glass workpiece function, and it is by refractive index between 1.4-1.7, and preferably the material between 1.45-1.60 is made.
Sheet can be flat or crooked, and has any Dimension Types, and particularly at least one size is greater than 1 meter.
It advantageously is comprised of glass sheet.
Glass is soda lime type preferably, but other type of glass also can use such as Pyrex.Glass can be transparent or super transparent or chromatography, for example blue, green, the amber coppery or grey.
The thickness of glass sheet is usually between 0.5-19mm, especially between 2-12mm, or even between 4-8mm.
As modification, counter substrate 6 is by flexible clear materials, and for example plastics are made.
It should be noted, as a kind of modification, counter substrate 6 can have functional coat on the outside surface 6B all or part of at it.Functional coat is for example by photocatalysis coating, for example TiO
2Layer or hydrophilic coating form.
Laminated middle layer 10 is the films that consist of thermoplastic, for example by PU (polyurethane), is made, and has the refractive index between 1.4-1.7.It can also be by PVB, acoustics PVB, EVA or SGP (DuPont SentryGlas
Plus) make.
Laminated middle layer 10 has the thickness between 0.3-5mm usually.
Functional system 4 is electrochromic system advantageously.
Electrochromic system can be any suitable type.It is comprised of for example organic electroluminescence system of adding lustre to, wherein electrochromic material is electrochromic system organic, that mix, wherein electrochromic system is solid, more particularly there is inorganic nature, and the electrolyte of wherein separating electrochromic layer is organic, for example, with the form of gel or solution, or be solid-state electrochromic system in addition, wherein electrolyte is also inorganic layer and solid.
For example US-5239406 and EP-A-0612 826 describe the organic electrochromic system.
EP-0253713, EP-0670346, EP0382623, EP-0518754 or EP-0532408 describe the mixing electricity and cause the system of adding lustre to.
EP-0831360 and WO-A-00/03290 describe solid-state electrochromic system.
Yet, as a kind of modification, functional system 4 is gas-discoloration system or idle system, in order to obtain significant transmission in visible region, change, but not in other electromagnetic radiation zone, for example infrared.
Advantageously, functional system 4 is solid-state electrochromic systems.This system be comprised of inorganic layer has advantages of durable.This system also has advantages of that the number of substrates of making is minimum.
Usually, a solid-state electrochromic system for example comprises:
The first electrode coating of-formation on substrate 2, for example indium oxide based on doped tin (ITO);
-the first electrochromic material layer of forming on the first electrode coating, based on for example tungsten oxide;
-the electrolyte that forms on the first electrochromic material layer forms layer, based on for example tantalum oxide;
-form the second electrochromic material layer formed on layer at electrolyte, based on for example nickel oxide;
-the second electrode coating of forming on the second electrochromic material layer, based on for example ITO.
Apply electromotive force and make for example H between electrode coating
+Or Li
+Alkali metal ion embeds the first electrochromic layer, and makes ion from the second electrochromism pull-up embedding, causes functional system to be added lustre to.
Apply opposite potential and will cause same ion from the first electrochromism pull-up embedding, and cause ion to embed the second electrochromic layer, cause the decolouring of system.
This system has advantages of very repeatedly reversible and reversible through the year number more than 10 years, makes them can be used as the glass workpiece of building.
Yet the character that it should be noted that functional system has no significant effect adding lustre to of device in reflection.In fact, once functional system, with the electrode coating of the outside surface at glass workpiece and electrochemical activity interlayer, just exists and adds lustre in external reflection.The present invention that Here it is can be applicable to the reason of all types of functional system, and never is limited to solid-state electrochromic system.
Substrate 2 is the sheet that plays the glass workpiece effect, for example glass sheet.
In the same manner for counter substrate 6, its glass is soda lime type preferably, but other glass types, and for example borosilicate glass also can be used.Glass 2 can be transparent or super transparent or chromatography, for example blue, green, the amber coppery or grey.The thickness of glass sheet is usually between 0.5-19mm, especially between 2-12mm, or even between 4-8mm.
As modification, substrate 2 is made by flexible clear materials, for example is made of plastics.
Embodiment
Substrate 2 is soda lime glass sheet that 6mm is thick.
Functional system 4 is solid-state electrochromic systems, and its Direct precipitation, on substrate 2, and consists of following lamination, from substrate 2:
The ITO layer that 500nm is thick, it forms the iridium oxide layer that the first electrode coating/55nm is thick, it forms tungsten oxide and the thick tantalum oxide layers of 300nm of the first electrochromic layer/150nm, its form electrolyte/400nm thick mix H
+Tungsten oxide, it forms the ITO layer that the second electrochromic layer/100nm is thick, it forms the second electrode coating.
Laminated middle layer contacts with functional system 4.Laminated middle layer consists of 0.76 thick polyurethane sheet.
Reflex control coating 8 is Si that 70nm is thick
3N
4Layer.
Reflex control coating 8 Direct precipitations are on counter substrate 6.
Laminated middle layer 10 contacts with reflex control coating 8.
Thus, install 1 layout as follows:
(the buildings outside) 6mm glass sheet/70nm Si
3N
4The laminated middle layer of reflex control coating/0.76mm polyurethane/100nm ITO/400nm H
+The ITO layer that tungsten oxide/300nm tantalum oxide/150nm tungsten oxide/55nm yttrium oxide/500nm is thick of doping/6mm glass sheet.
Device 1 has following characteristic under the state that does not add lustre to and do not add lustre to:
Do not add lustre to
Add lustre to
Table 1
R
LIt is luminous reflectivity.Usually adopt CIE D65 standard sources and 2 ° of observers of standard to determine.System (L, a
*, b
*) be conventional.It is corresponding to the standard of CIE S 014-4/E:2007 and iso standard 11664-4:2008 (E) definition.This system defines intensity value C especially
*.
Should remember C
*Corresponding to coordinate (a
*, b
*) the mould (norm) of vector, that is to say,
It should be noted, the function lamination is not limited to as mentioned above.The example that another solid-state electricity causes the system of adding lustre to be Direct precipitation on substrate 2, and formed by following lamination, from substrate 2: float glass (2.3mm)/ZrOx or NbOx 10nm/SiO
230nm/ITO (250-500nm)/WOx 410nm/ZrOx or NbOx 60nm/W-NiOx 300nm/ITO (250-500nm)/SnO
230nm/SiO
260nm.
In addition, theme of the present invention is the glass workpiece that contains apparatus of the present invention 1.Described glass workpiece is comprised of for example following structure for glass workpiece:
1. single-glass part, wherein two glass sheet laminated be single glass part pane: (the buildings outside) glass sheet/reflex control coating/laminated middle layer/functional system/glass sheet;
2. double glazing part, wherein two in three glass sheet are laminated and form laminated glass part pane: (the buildings outside) glass sheet/reflex control coating/laminated middle layer/functional system/glass sheet/filling is as the space/low-emissivity coating of the gas of argon or krypton/glass sheet (buildings inboard);
3. triplex glass part, wherein two in four glass sheet are laminated together: (the buildings outside) glass sheet/reflex control coating/laminated middle layer/functional system/glass sheet/filling as the space/glass sheet of the gas of argon or krypton/filling as the space/low-emissivity coating of the gas of argon or krypton/glass sheet (buildings inboard);
4. triplex glass part, wherein two in four glass sheet are laminated and form laminated glass part pane: (the buildings outside) glass sheet/reflex control coating/laminated middle layer/functional system/glass sheet/filling as the space/antireflection coatings of the gas of argon or krypton/glass sheet/antireflection coatings/filling as the space/low-emissivity coating of the gas of argon or krypton/glass sheet (buildings inboard);
5. double glazing part, wherein two in four glass sheet are laminated and form laminated glass part pane: (the buildings outside) glass sheet/reflex control coating/laminated middle layer/glass sheet/functional system/fillings as the space/low-emissivity coating of the gas of argon or krypton or air or oxygen-optionally-/glass sheet (buildings inboard);
6. triplex glass part, wherein two of four glass sheet laminated and form laminated glass part pane: (the buildings outside) glass sheet/reflex control coating/laminated middle layer/glass sheet/functional system/fillings as each mask on its two sides of the space/glass sheet of the gas of argon or krypton or air or oxygen-alternatively have antireflection coatings-/filling is as the space/low-emissivity coating of the gas of argon or krypton/glass sheet (buildings inboard);
7. single-glass part, wherein three glass sheet are laminated and form laminated glass part pane: (the buildings outside) glass sheet/reflex control coating/laminated middle layer/glass sheet/functional system/functional system/glass sheet (buildings inboard);
8. double glazing part, wherein three in four glass sheet are laminated and form laminated glass part pane: (the buildings outside) glass sheet/reflex control coating/laminated middle layer/glass sheet/functional system/glass sheet/filling is as the space/low-emissivity coating of the gas of argon or krypton/glass sheet (buildings inboard);
9. triplex glass part, wherein three in five glass sheet are laminated and form laminated glass part pane: (the buildings outside) glass sheet/reflex control coating/laminated middle layer/glass sheet/functional system/glass sheet/filling as the space/glass sheet of the gas of argon or krypton/filling as the space/low-emissivity coating of the gas of argon or krypton/glass sheet (buildings inboard);
10. single-glass part, wherein two glass sheet and two plastic plates are laminated and form laminated glass part pane: (the buildings outside) glass sheet/reflex control coating/laminated middle layer/plastic plate/functional system/plastic plate/laminated middle layer/glass sheet (buildings inboard);
11. the double glazing part, wherein two in three glass sheet and two plastic plates are laminated and form laminated glass part pane: (the buildings outside) glass sheet/reflex control coating/laminated middle layer/plastic plate/functional system/plastic plate/laminated middle layer/glass sheet/filling is as the space/low-emissivity coating of the gas of argon or krypton/glass sheet (buildings inboard);
12. the triplex glass part, wherein two in five glass sheet and two plastic plates are laminated to form laminated glass part pane: (the buildings outside) glass sheet/reflex control coating/laminated middle layer/plastic plate/functional system/plastic plate/laminated middle layer/glass sheet/filling as the space/glass sheet of the gas of argon or krypton/filling as the space/low-emissivity coating of the gas of argon or krypton/glass sheet (buildings inboard);
Usually, glass workpiece comprises laminated glass workpiece pane.This laminated glass part is designed to be arranged in the buildings outside.
The double glazing part is interpreted as meaning the assembly of glass workpiece pane two intervals and that separated by gas or vacuum space, and the triplex glass part is interpreted as meaning the assembly of glass workpiece pane three intervals and that separated by two gases or vacuum space.As mentioned above, the glass pane at least one interval of compound glass part is laminated.
In all structures, the glass sheet in the outside is counter substrate 6.
In structure 1-4, glass workpiece comprises laminated glass workpiece pane, and it is disposed in the outside and adds functional system.The substrate here is second glass sheet from the outside.This functional system is for example solid-state electrochromic system.
In structure 5 and 6, functional system forms on laminated glass part inside surface, and it faces inboard.This functional system is separated by the gas space and ensuing glass sheet.This functional system is for example solid-state electrochromic system.Substrate is second glass sheet from the outside.
In structure 7-12, functional system forms on two substrates.It for example by mix or completely the organic electrochromic system form.In both of these case, the first electrode coating of this functional system forms on first substrate, and the second electrode coating of this functional system forms on second substrate.Second and the 3rd glass sheet that plays the glass pane effect at this from the outside is respectively first substrate and second substrate.
Yet it should be noted that as explained above, the electrochromic system that device according to the present invention comprises can comprise that one or more transparent conducting coatings are as SnO
2: F or ITO and/or one or more conductive network as metal wire.Electrochemical activity layer and one or more dielectric substrate can gelling solns and/or the form of the form of conducting polymer and/or the one or more inorganic layers by magnetron cathode sputter, DVD or sol-gel process deposition, and this does not deviate from center of the present invention.
In addition, invention purpose is to manufacture the method for described device.
According to the present invention, said method comprising the steps of:
-formation the first electrode coating on substrate;
-form the second electrode coating;
-forming at least one electrochemical activity layer, it is designed between the first electrode coating and the second electrode coating;
-formation reflex control coating on the inside surface of counter substrate;
-laminated the middle layer that will be made by polymeric material is for laminated counter substrate, and laminated middle layer is between reflex control coating and functional system.
By laminated middle layer, implement laminated.Typically, by described device being heated to approximately 120 ℃ of temperature, within 15 minutes, obtain, but have the possibility of many heating.
The device obtained by described method demonstrates all above-mentioned characteristics.
Claims (14)
1. a device (1), it comprises:
-substrate (2);
-have can be automatically controlled optics and/or the electrochemical function system (4) of energy characteristics, this functional system (4) comprising:
-at upper the first electrode coating formed of substrate (2);
The-the second electrode coating, and
At least one electrochemical activity layer, its between the first electrode coating and the second electrode coating, at least one active electrochemical layer can the first state and and the first state there is different optical and/or energy and transmit between the second state of performance and reversibly change;
-counter substrate (6), it is designed to be arranged on the outside of incident sunlight one side with respect to substrate (2);
-reflex control coating (8), it is for decaying/change the color of lateral reflection device outwardly; Reflex control coating (8) is in the upper formation of the inside surface (6A) of counter substrate (6), and reflex control system (8) plays the colorimeter system (L that reduces device described in reflection
*, a
*, b
*) middle C
*The effect of intensity value;
-laminated middle layer (10), it is made by polymeric material, and be inserted between reflex control coating (8) and functional system (4), counter substrate (6) and laminated middle layer (10) have the refractive index between 1.4-1.7 and are greater than 20 μ m, for example be greater than the thickness of 100 μ m, for example, for laminated middle layer (10), its thickness is greater than 300 μ m, and for example for counter substrate (6), its thickness is greater than 500 μ m, reflex control coating (8) has refractive index and the thickness through selecting, C when to make incident angle with respect to the normal (N) of the outside surface (6B) of counter substrate (6) be 60 ° and 8 °
*be less than or equal to 10, and the C of incident angle while being 8 °
*C when value and incident angle are 60 °
*the absolute value of the difference of value is less than or equal to 6.
2. the device of claim 1 (1), wherein reflex control coating (8) has refractive index and the thickness through selecting, C when to make incident angle with respect to the normal (N) of the outside surface (6B) of counter substrate (6) be 8 ° and 60 °
*For being less than or equal to 10.
3. claim 1 or 2 device (1), wherein reflex control coating (8) comprises the individual layer of material.
4. the device (1) of any one in aforementioned claim, wherein reflex control coating (8) contacts with the inside surface (6A) of counter substrate (6).
5. the device (1) of any one in aforementioned claim, wherein reflex control coating (8) contacts with the outside surface (10B) of laminated middle layer (10).
6. the device (1) of any one in aforementioned claim, wherein reflex control coating (8) comprises that refractive index is between 1.6-2.4, preferably between 1.75-2.15, preferably between 1.90-2.05 the layer, the thickness of reflex control coating (8) is between 60-110nm, preferably between 60-90nm.
7. the device (1) of any one in aforementioned claim, wherein the reflection coefficient of reflex control coating (8) is more than or equal to 10%, preferably between 12-25%.
8. claim 7 or 8 device (1), wherein reflex control coating (8) consists of one or more materials, and described material is selected from following: several combination in the titanium dioxide of the indium oxide of silicon nitride, tin oxide, silicon oxynitride, zinc paste, aluminium nitride, doped tin (ITO), tin/zinc mixed oxide, titanium dioxide, doping zinc, the titanium dioxide of doped silicon or these materials.
9. the device (1) of any one in aforementioned claim, the refractive index of counter substrate (6) and laminated middle layer (10) is between 1.45-1.60.
10. the device (1) of any one in aforementioned claim, wherein laminated middle layer (10) are the films consisted of thermoplastic, for example, by PU (polyurethane), PVB, acoustics PVB, EVA or SGP (DuPont SentryGlas
Plus) make.
11. the device of any one (1) in aforementioned claim, wherein said functional system is electrochromic system, and at least one electrochemical activity layer is electrochromic.
12. the device of claim 11 (1), wherein electrochromism functional system (4) has solid-state type.
13. a glass workpiece pane, it comprises that at least one has the sheet of glass workpiece function, the device (1) that wherein it comprises any one in aforementioned claim, and substrate (2) and counter substrate (6) they are the sheets with glass workpiece function.
14. the method for a manufacturing installation (1), it comprises the following steps:
-at upper first electrode coating that forms of substrate (2);
-form the second electrode coating;
-form design at least one electrochemical activity layer between the first electrode coating and the second electrode coating, at least one electrochemical activity layer can the first state and and the first state have between the second state of different optical transmission and/or energy characteristics and reversibly change;
-be formed for changing/decay the reflex control coating (8) of the color of device (1) in lateral reflection outwardly, reflex control coating (8) is in the upper formation of the inside surface (6A) of counter substrate (6), counter substrate (6) is designed to be arranged on the outside of incident sunlight one side with respect to substrate (2), and reflex control coating (8) plays the colorimeter system (L that reduces device (1) in reflection
*, a
*, b
*) middle C
*The effect of intensity value;
-laminated the middle layer (10) that will be made by polymeric material is for laminated counter substrate (6), laminated middle layer (10) is between reflex control coating (8) and functional system (4), counter substrate (6) and laminated middle layer (10) have the refractive index between 1.4 and 1.7, with be greater than 20 μ m, for example be greater than the thickness of 100 μ m, for example, for laminated middle layer (10), its thickness is greater than 300 μ m, and for example for counter substrate (6), its thickness is greater than 500 μ m, reflex control coating (8) has refractive index and the thickness through selecting, C when to make incident angle with respect to the normal (N) of the outside surface (6B) of counter substrate (6) be 60 ° and 8 °
*be less than or equal to 10, and the C of incident angle while being 8 °
*C when value and incident angle are 60 °
*the absolute value of the difference of value is less than or equal to 6.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1054921 | 2010-06-21 | ||
| FR1054921A FR2961609B1 (en) | 2010-06-21 | 2010-06-21 | DEVICE HAVING ELECTRO-CONTROLLABLE OPTICAL AND / OR ENERGY PROPERTIES |
| US37710910P | 2010-08-26 | 2010-08-26 | |
| US61/377,109 | 2010-08-26 | ||
| PCT/EP2011/060363 WO2011161110A1 (en) | 2010-06-21 | 2011-06-21 | Electrochromic device with anti-iridescent coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103430089A true CN103430089A (en) | 2013-12-04 |
| CN103430089B CN103430089B (en) | 2016-10-12 |
Family
ID=43086078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180040599.6A Active CN103430089B (en) | 2010-06-21 | 2011-06-21 | There is the electrochromic device of anti-iridescent coating |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US9091896B2 (en) |
| EP (1) | EP2583135B1 (en) |
| CN (1) | CN103430089B (en) |
| FR (1) | FR2961609B1 (en) |
| WO (1) | WO2011161110A1 (en) |
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| CN107732024A (en) * | 2016-08-11 | 2018-02-23 | 三星显示有限公司 | Display device |
| CN111108435A (en) * | 2017-09-29 | 2020-05-05 | 法国圣戈班玻璃厂 | Coloured PVB |
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| US8164818B2 (en) * | 2010-11-08 | 2012-04-24 | Soladigm, Inc. | Electrochromic window fabrication methods |
| US10739658B2 (en) | 2011-12-12 | 2020-08-11 | View, Inc. | Electrochromic laminates |
| KR20150067311A (en) * | 2012-11-08 | 2015-06-17 | 쌩-고벵 글래스 프랑스 | Glazing having switchable optical properties |
| WO2015000534A1 (en) * | 2013-07-05 | 2015-01-08 | Essilor International (Compagnie Generale D'optique) | Optical article comprising an antireflective coating with a very low reflection in the visible region |
| NL2012607B1 (en) * | 2014-04-11 | 2016-05-09 | Aviation Glass & Tech Holding B V | Vehicle mirror, and method for manufacturing such a mirror. |
| US10108067B2 (en) * | 2014-12-26 | 2018-10-23 | National Institute Of Advanced Industrial Science And Technology | Gasochromic dimming mechanism |
| EP3446178A4 (en) | 2016-04-19 | 2020-01-22 | Sage Electrochromics, Inc. | Electrochromic device including a transparent conductive oxide layer and a bus bar and a process of forming the same |
| KR101926960B1 (en) * | 2017-02-10 | 2018-12-07 | 주식회사 케이씨씨 | Low Reflection Coating Glass |
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| CN111278783A (en) | 2017-11-06 | 2020-06-12 | Sage电致变色显示有限公司 | Article comprising a non-luminescent variable transmission device and a coating |
| WO2019219595A1 (en) * | 2018-05-14 | 2019-11-21 | Agc Glass Europe | Asymmetrical vacuum-insulated glazing unit |
| FR3105460B1 (en) * | 2019-12-24 | 2023-01-20 | Saint Gobain | Optical system with electrochemical functional device having electrically controllable optical and/or energetic properties and chromatic control coating in reflection, related methods. |
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| US11287717B2 (en) | 2020-04-09 | 2022-03-29 | Glass Dyenamics | Variable light transmission structures with improved optical properties |
| KR20220131448A (en) * | 2021-03-19 | 2022-09-28 | 현대자동차주식회사 | Glass for Vehicle |
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Also Published As
| Publication number | Publication date |
|---|---|
| FR2961609B1 (en) | 2012-06-01 |
| EP2583135B1 (en) | 2015-01-07 |
| FR2961609A1 (en) | 2011-12-23 |
| WO2011161110A1 (en) | 2011-12-29 |
| US9091896B2 (en) | 2015-07-28 |
| EP2583135A1 (en) | 2013-04-24 |
| US20140085701A1 (en) | 2014-03-27 |
| CN103430089B (en) | 2016-10-12 |
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